Enantiodivergent Atroposelective Synthesis of Chiral Biaryls by Asymmetric Transfer Hydrogenation: Chiral Phosphoric Acid Catalyzed Dynamic Kinetic Resolution

Reported herein is an enantiodivergent synthesis of chiral biaryls by a chiral phosphoric acid catalyzed asymmetric transfer hydrogenation reaction. Upon treatment of biaryl lactols with aromatic amines and a Hantzsch ester in the presence of chiral phosphoric acid, dynamic kinetic resolution (DKR)...

Full description

Saved in:
Bibliographic Details
Published inAngewandte Chemie Vol. 128; no. 38; pp. 11814 - 11818
Main Authors Mori, Keiji, Itakura, Tsubasa, Akiyama, Takahiko
Format Journal Article
LanguageEnglish
German
Published Weinheim Blackwell Publishing Ltd 12.09.2016
Wiley Subscription Services, Inc
Subjects
Adducts
Amination
Amines
Asymmetry
Biaryle
Biphenyl
Chemical industry
Chemical synthesis
Chemistry
Derivatives
Dynamics
Enantioselektivität
Hydrierungen
Hydrogenation
Isomers
Kinetische Racematspaltung
Organokatalyse
Phosphoric acid
Reaction kinetics
Substrates
Synthesis
Online AccessGet full text

Cover

More Information
Summary:Reported herein is an enantiodivergent synthesis of chiral biaryls by a chiral phosphoric acid catalyzed asymmetric transfer hydrogenation reaction. Upon treatment of biaryl lactols with aromatic amines and a Hantzsch ester in the presence of chiral phosphoric acid, dynamic kinetic resolution (DKR) involving a reductive amination reaction proceeded smoothly to furnish both R and S isomers of chiral biaryls with excellent enantioselectivities by proper choice of hydroxyaniline derivative. This trend was observed in wide variety of substrates, and various chiral biphenyl and phenyl naphthyl adducts were synthesized with satisfactory enantioselectivities in enantiodivergent fashion. The enantiodivergent synthesis of synthetically challenging, chiral o‐tetrasubstituted biaryls were also accomplished, and suggests high synthetic potential of the present method. Divergierend: Bei der Titelreaktion führt die Behandlung von Biaryl‐Lactolen mit aromatischen Aminen und einem Hantzsch‐Ester in Gegenwart eines chiralen Phosphorsäurederivats zur dynamischen kinetischen Racematspaltung durch reduktive Aminierung. Je nach Wahl des Hydroxyanilinderivats sind sowohl die R‐ als auch die S‐Isomere der chiralen Biaryle zugänglich. M.S.=Molekularsieb.
Bibliography:ArticleID:ANGE201606063
Grant-in-Aid for Scientific Research
Grant-in Aid for Scientific Research
ark:/67375/WNG-SN5X3F81-B
istex:0A7702A2D94B5DBBCEAEE8940A56F443188A9529
Ministry of Education, Culture, Sports, Science and Technology, Japan
Japan Society for the Promotion of Science
ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201606063